CN115594195A - Method for preparing phosphorus-modified H-ZSM-5 molecular sieve by solid phase method - Google Patents
Method for preparing phosphorus-modified H-ZSM-5 molecular sieve by solid phase method Download PDFInfo
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- CN115594195A CN115594195A CN202211480515.7A CN202211480515A CN115594195A CN 115594195 A CN115594195 A CN 115594195A CN 202211480515 A CN202211480515 A CN 202211480515A CN 115594195 A CN115594195 A CN 115594195A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000010532 solid phase synthesis reaction Methods 0.000 title claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 229910021485 fumed silica Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical group [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 ethylene, propylene Chemical group 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical Kinetics & Catalysis (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing a phosphorus-modified H-ZSM-5 molecular sieve by a solid phase method in one step, which comprises the following steps: fully grinding a silicon source, an aluminum source, a phosphorus source, an organic template agent and an alkalinity regulator according to a certain proportion to obtain powder, transferring the powder into a reaction kettle for crystallization, recovering the crystallized product, calcining to remove the template agent, immersing the product into an ammonia salt solution for ion exchange, and calcining at a high temperature to obtain the phosphorus-modified H-ZSM-5 molecular sieve material. The invention avoids the problems of complex preparation process, environmental pollution and uneven phosphorus load of the traditional hydrothermal synthesis, improves the catalytic performance of the H-ZSM-5 molecular sieve, and has longer catalytic life and higher olefin selectivity.
Description
Technical Field
The invention relates to the technical field of molecular sieves and preparation thereof, in particular to a method for preparing a phosphorus-modified H-ZSM-5 molecular sieve by a solid phase method.
Background
The low-carbon olefin such as ethylene, propylene and the like is used as an important basic raw material and has important application in the fields of modern petrochemical industry, fine chemical processing synthesis and the like. In the past, ethylene and propylene were mostly obtained by means of petroleum cracking under high temperature conditions. However, with the increasing shortage and shortage of petroleum resources, people are gradually forced to find a way for producing and preparing low-carbon olefins without depending on petroleum resources. Up to now, methanol To Olefin (MTO) reaction, one of the most important C1 chemical reactions, is considered to be the most successful method for producing low carbon olefins by non-petroleum routes. The catalyst is a key factor in regulating the MTO product distribution. The ZSM-5 molecular sieve with the MFI structure becomes one of main catalysts of the MTO reaction due to the abundant pore structure, the regular pore channel distribution, the large specific surface area, the high thermal stability and the high hydrothermal stability. Compared with other catalysts of MTO reaction, the ZSM-5 molecular sieve shows longer catalytic life and lower selectivity of low-carbon olefin. The conventional phosphorus-modified ZSM-5 molecular sieve is usually synthesized into the ZSM-5 molecular sieve by a hydrothermal method and then phosphorus is introduced into the ZSM-5 molecular sieve by a soaking method, so that the problems of potential autogenous pressure hazard, product yield problem, water pollution, uneven phosphorus element load and the like caused by a reaction kettle are solved.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art and providing a green and environment-friendly method for preparing a high-performance H-ZSM-5 molecular sieve, which solves the problems of complex preparation process, environmental pollution and uneven phosphorus load of the traditional phosphorus-modified H-ZSM-5 molecular sieve.
In order to solve the technical problems, the invention provides a method for preparing a phosphorus-modified H-ZSM-5 molecular sieve by one step by a solid phase method. The invention comprises the following steps:
(1) Mixing a silicon source, an aluminum source, a phosphorus source, an organic template agent and an alkalinity regulator, putting the mixture into a planetary ball mill, fully grinding the mixture for 10 to 30 min at the rotating speed of 100 to 200r/min, transferring the obtained powder into a stainless steel hydrothermal kettle, crystallizing the powder for 36 to 60 h at the temperature of 150 to 180 ℃, recovering the product, calcining the product at the high temperature of 450 to 600 ℃ in a muffle furnace for 4 to 15 h, and removing the template agent to obtain the phosphorus modified Na-ZSM-5 molecular sieve.
(2) Immersing the Na-ZSM-5 molecular sieve obtained in the step (1) in 0.5-2.0 mol/L ammonia salt solution, performing ion exchange for 2~3 times at 70-90 ℃ for 2-3 h each time, and then performing suction filtration, washing and drying to obtain NH 4 -a ZSM-5 molecular sieve, and calcining the molecular sieve at the high temperature of 450 to 600 ℃ in a muffle furnace for 4 to 6 hours to obtain the phosphorus-modified H-ZSM-5 molecular sieve.
As an improvement, the silicon source is one or more of sodium silicate nonahydrate, silica gel microspheres, fumed silica and white carbon black.
As an improvement, the aluminum source is one of pseudo-boehmite, sodium metaaluminate and aluminum sulfate.
As an improvement, the alkalinity regulator is one of ammonium chloride, ammonium nitrate and ammonium fluoride.
The improvement is that the phosphorus source is one of phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
As an improvement, the organic template agent is tetrapropylammonium bromide.
As an improvement, the ammonium salt is one of ammonium chloride and ammonium nitrate.
The invention also provides the H-ZSM-5 molecular sieve prepared by any one of the preparation methods. The molar ratio of a silicon source to an aluminum source of the H-ZSM-5 molecular sieve is 200 to 25, the molar ratio of the silicon source to the template is 20 to 1 to 5, and the molar ratio of the phosphorus source to the silicon source is 0.01 to 0.04.
The invention has the beneficial effects that: (1) The use of the solid phase method avoids the problems of autogenous pressure, water pollution and the like generated by the traditional hydrothermal synthesis. (2) The phosphorus source is not introduced into the molecular sieve by a soaking method, but is added in the synthesis process of the H-ZSM-5 molecular sieve, so that the phosphorus source uniformly participates in the growth of the molecular sieve crystal, and the problem of phosphorus element accumulation possibly caused in the soaking process is avoided. (3) The phosphorus modified Na-ZSM-5 molecular sieve is synthesized by one step through a solid phase method, so that the synthesis steps are simplified, and the research on the synthesis process of the modified molecular sieve is a very favorable progress.
Drawings
FIG. 1 is an XRD pattern for comparative example 1, example 1~4;
FIG. 2 is an SEM image of example 2 and comparative example 4~5;
FIG. 3 is a diagram of the distribution of elements of example 2.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
Example 1
9.5g sodium silicate nonahydrate, 2g fumed silica, 1.8g tetrapropylammonium bromide, 2.85g ammonium chloride, 0.17g sodium metaaluminate, and 0.076 g ammonium dihydrogen phosphate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 48 h. Calcining the obtained product at 550 ℃ in a muffle furnace to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and carrying out NH treatment on the Na-ZSM-5 molecular sieve at the concentration of 1 mol/L 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
Comparative example 1
9.5g sodium silicate nonahydrate, 2g fumed silica, 1.8g tetrapropylammonium bromide, 2.85g ammonium chloride and 0.17g sodium metaaluminate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 48 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; finally, the product is filtered, washed and dried, and is calcined in a muffle furnace at 550 ℃ to obtain 6H and H-ZSM-5And (5) screening by using a secondary screen.
Comparative example 2
9.5g sodium silicate nonahydrate, 2g fumed silica, 1.8g tetrapropylammonium bromide, 2.85g ammonium chloride and 0.17g sodium metaaluminate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 36 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
Comparative example 3
9.5g sodium silicate nonahydrate, 2g fumed silica, 1.8g tetrapropylammonium bromide, 2.85g ammonium chloride and 0.17g sodium metaaluminate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ of 60 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
Example 2
9.5g sodium silicate nonahydrate, 2g fumed silica, 1.8g tetrapropylammonium bromide, 2.85g ammonium chloride, 0.17g sodium metaaluminate, and 0.15 g ammonium dihydrogen phosphate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 48 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged for each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
Comparative example 4
9.5g sodium silicate nonahydrate, 2g fumed silica, 5.4 g tetrapropyl hydroxideAmmonium, 2.85g ammonium chloride, 0.17g sodium metaaluminate and 0.15 g ammonium dihydrogen phosphate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 48 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
Comparative example 5
9.5g sodium silicate nonahydrate, 2g fumed silica, 5.4 g tetrapropylammonium hydroxide, 2.85g ammonium chloride, 0.17g sodium metaaluminate, and 0.15 g phosphoric acid were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 48 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
Example 3
9.5g sodium silicate nonahydrate, 2g fumed silica, 1.8g tetrapropylammonium bromide, 2.85g ammonium chloride, 0.17g sodium metaaluminate, and 0.23 g ammonium dihydrogen phosphate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 48 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
Example 4
9.5g sodium silicate nonahydrate, 2g fumed silica, 1.8g tetrapropylammonium bromide, 2.85g amine chloride, 0.17g sodium metaaluminate and 0.3 g ammonium dihydrogen phosphate were ground in a planetary ball mill at a rate of 100 r/min for 20 min. Then the mixed product is placed in a stainless steel hydrothermal kettle for solid phase crystallization at 180 ℃ to obtain 48 h. Calcining the obtained product in a muffle furnace at 550 ℃ to obtain 6 h, wherein the obtained product is the Na-ZSM-5 molecular sieve, and placing the Na-ZSM-5 molecular sieve in 1 mol/L NH 4 Ion exchange is carried out for 2 times in Cl solution at 85 ℃, and 3 h is exchanged each time; and finally, carrying out suction filtration, washing and drying on the product, and calcining the product in a muffle furnace at 550 ℃ to obtain the 6H to obtain the H-ZSM-5 molecular sieve.
FIG. 1 is an XRD pattern for comparative example 1, example 1~4. Comparative example 1~3 had no phosphorus source, example 1~4 and comparative example 4~5 had a phosphorus source. From this figure it can be found that: the samples prepared in the examples have distinct and sharp characteristic peaks of the H-ZSM-5 molecular sieve at 2 θ =7.9 °, 8.7 °, 14.7 °, 23.0 °, 23.9 ° and 24.3 °, indicating that the method produces the H-ZSM-5 molecular sieve with good crystallinity.
FIG. 2 is an SEM image of the H-ZSM-5 molecular sieve obtained in example 2 and comparative example 4~5, from which it can be found that: the morphology of the sample prepared by the embodiment presents a spheroid with stacked lamellar crystals, and the unique structure is favorable for improving the catalytic performance of the H-ZSM-5 molecular sieve. Compared with the molecular sieve prepared by the conventional hydrothermal method, the molecular sieve prepared by the technology has longer catalytic life and higher olefin selectivity in the catalytic reaction of preparing olefin from methanol.
FIG. 3 is the element distribution diagram of example 2, and it can be found from the diagram that the distribution of phosphorus element is consistent with that of silicon-aluminum element, and is more uniformly distributed in the molecular sieve crystal, which indicates that phosphorus is uniformly doped into H-ZSM-5 molecular sieve.
The technical solutions of the present invention are described in detail in the above examples, it should be understood that the examples are only specific examples of the present invention and are not intended to limit the present invention, and any modifications and improvements made within the principle scope of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a phosphorus modified H-ZSM-5 molecular sieve by a solid phase method is characterized by comprising the following steps:
(1) Mixing and grinding a silicon source, an aluminum source, a phosphorus source, an organic template and an alkalinity regulator, transferring the obtained powder into a reaction kettle for crystallization, and calcining the product after crystallization recovery to obtain a phosphorus modified Na-ZSM-5 molecular sieve;
(2) Immersing the phosphorus modified Na-ZSM-5 molecular sieve into an ammonia salt solution for ion exchange, and then carrying out suction filtration, washing and drying to obtain NH 4 -ZSM-5 molecular sieve, and calcining to obtain the phosphorus modified H-ZSM-5 molecular sieve.
2. The production method according to claim 1, characterized in that: in the step (1), the silicon source is one or more of sodium silicate nonahydrate, silica gel microspheres, fumed silica and white carbon black; the aluminum source is one of pseudo-boehmite, sodium metaaluminate and aluminum sulfate; the phosphorus source is one of phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate; the organic template agent is tetrapropylammonium bromide; the alkalinity regulator is one of ammonium chloride, ammonium nitrate and ammonium fluoride.
3. The method of claim 1, wherein: in the step (1), a planetary ball mill is selected as the grinding equipment, the grinding speed is 100 to 200r/min, and the grinding time is 10 to 30 min.
4. The method of claim 1, wherein: in the step (1), a stainless steel hydrothermal kettle is selected as the reaction kettle, the crystallization temperature is 150 to 180 ℃, and the crystallization time is 36 to 60 hours.
5. The method of claim 1, wherein: in the step (1), a muffle furnace is selected as the equipment for calcination, the calcination temperature is 450 to 600 ℃, and the calcination time is 4 to 15 hours.
6. The method of claim 1, wherein: in the step (2), the concentration of the ammonium salt solution is 0.5 to 2.0mol/L, and the ammonium salt is one of ammonium chloride and ammonium nitrate.
7. The method of claim 1, wherein: in the step (2), the temperature of the ion exchange is 70 to 90 ℃, the ion exchange frequency is 2~3, and each time is 2 to 3 hours.
8. The method of claim 1, wherein: in the step (2), a muffle furnace is selected as the calcining equipment, the calcining temperature is 450-600 ℃, and the calcining time is 4-6 h.
9. An H-ZSM-5 molecular sieve, characterized in that: the method of claim 1~8.
10. The H-ZSM-5 molecular sieve of claim 9, wherein: the molar ratio of a silicon source to an aluminum source in the H-ZSM-5 molecular sieve is 200 to 25, the molar ratio of the silicon source to a template is 20 to 5.
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| CN116477640A (en) * | 2023-05-16 | 2023-07-25 | 中国矿业大学 | Method for directly preparing phosphorus modified H-type ZSM-5 molecular sieve by solid phase method |
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